Antifouling paint



United States Patent ANTIFOULING PAINT Yushiro Shiraishi, Ashiya City, Hyogo-ken, Japan, as-

signor to Osaka Kinzoku Kogyo Company, Limited, Osaka, Japan No Drawing. Application June 14, 1955,

Serial No. 515,528-

Claims priority, application Japan June 23, 1954 4 Claims. (Cl. 106-15) This invention relates to an antifouling paint and has for its object to obtain a paint which is less injurious to a person and maintains its antifouling property for a long period without decomposition and flowing of the effective ingredients.

An antifouling paint according to this invention comprises as the antifouling ingredients one or more w-flllOl'O aliphatic compounds such as F(CH2)21L 1COOH, F(CHz)2nOH and their derivatives, where n is an integral number larger than 1.

The abovementioned fluoro compounds are called generally as fluoroacetates and they are obtained by the reaction of the corresponding halogen compounds with fluoride of silver, mercury, antimony or potassium, respectively, or derived from other fluoro compounds. The aliphatic compounds in which an atom of fluorine is combined at w-position, show the characteristic antifouling effeet, while the compounds in which an atom of fluorine being combined at any position other than w-position or in which two or more atoms of fluorine are combined, lose almost all antifouling effect. On the other hand, the compounds of which n is the abovementioned formula is 3, show the highest antifouling effect. So in my invention, w-fluoro aliphatic compounds of which n is one to six, are preferably used. As w-flIlOl'O aliphatic compounds, I can use acids, alcohols and their derivatives such as salts, nitriles, esters, ethers, acetals, amides, hydrazides, ketones, aldehydes and amines; the important compounds are mentioned as follows:

2-fluoroethanol F(CH2)2OH. 4-fluorobutanol F(CH2)4OH. Z-fluoroethyl fluoroacetate.. F CHzCOO (CH2)2F. 2-chloroethyl fluoroacetate FCH2COO(CH2)2C1. Z-fluoroethyl 5-fluorocapronate. F (CH2)5COO(CH2)2F.

Glycol bisfiuoroacetate (FCH2COO)2C2H4. Glycerol trisfluoroacetate (FCH2COO)3C3H5. Fluoroacetic acid F CHzCOOH.

3-fluoro butyric acid F(CH2)3COOH. Fluoroacetoaldehyde FCHaCHO. Fluoroacetone FCHaCOCI-Is. 2-2' difluoroethylether F(CH2)2O(CH2)2F.

Bis fluoroethylacetal CH3-CH(OCH2CH2F)2. Fluoroacetoamide FCHaCONHz. Fluoroacetoanilide", FCH2CONHC Phenylhydrazine fluoroacetate FCH2CONHNHO 1-amino-2-fluoroethane F(CH2)2NH. Fluoroacetonitrile FCHzCN.

Sodium fiuoroacetate FCH2COONa.

Barium fluoroacetate (FCH2COO)2Ba.

They are colorless and transparent liquids or crystals and some of them have a faint ester odor. Most of them dissolve easily in alcohols, ethers, aldehydes and esters, especially easily in animal and vegetable oils and fats and varnishes. By reason of their oil solubility or great affinity for oil, the paint obtained is characterized by the absence of separation of the effective ingredients, and ease Patented July 23, 1957 ice of application. The usual antifouling paints containing heavy metals, such as copper, mercury or compounds of these metals, as the antifouling ingredients have a tendency to separate out, and are diflicult to apply, especially by spray-coating.

The said w-fluoro compounds show high toxic character for all animals, and are particularly fatal to insects and shell-fishes even at extremely low concentration, but they show on a person relatively low toxic character without accumulative property such as the toxic symptom due to heavy metal. Moreover; because of the very stable combination of fluorine atom with carbon atom, the said compound is also very stable and does not lose its toxic character for a long period even in sea water. Accordingly, the paint of my invention shows high antifouling eflect for a long period of more than eight months by the stability and absence of flowing of the eifective ingredients.

In my invention, an antifouling paint is obtained by kneading said w-flllOro aliphatic compound, pigment and varnish in a milling machine. As the antifouling ingredient, one or more compounds of the abovementioned w-fluoro compounds such as acid, alcohol, salt, nitrile, ester, ether, acetal, amide, hydrazide, ketone, aldehyde and amine are used, and oil varnish, natural and artificial resin, shellac and also coal tar, pitch, wood tar are used as varnish in this paint. The usual antifouling ingredient such as cuprous oxide, mercuric oxide and pentachlorphenol may be mixed in my paint, and also my paint may be mixed with the usual antifouling paint.

Example 1 Parts 2-fluoroethyl fluoroacetate 10 Pigment 45 Oil varnish 45 Example 2 Parts 2-fluoroethyl 5-fluorocapronate 3 Pigment 45 Polyvinyl varnish 52 Example3 Parts Glycol bisfiuoroacetate 15 Pigment 45 Shellac varnish 40 Example4 Parts Monofluoroacetamide 15 Solid cream of zinc oxide 45 Shellac varnish 40 Example5 Parts Phenylhydrazine fluoroacetate 10 Solid cream of zinc oxide 45 Artificial resin (polymerized benzyl chloride) 15 Benzol 30 Example 6 Parts Copper monofluoroacetate 20 Pigment 30 Oil varnish 50 In each of the abovementioned examples, all materials were mixed and kneaded in a milling machine and the antifouling paint was obtained.

An iron plate was coated with the paint obtained and steeped in sea water. The plate was completely protected from the adhesion of shell-fish and other marine organisms for eight months.

SEARCH Gist What I claim is:

1. An anti-fouling paint consisting essentially of varnish, pigment and an w-fluoroalkyl compound selected from the group consisting of w-fluoroalkanoic acids, w-fillOl'O- alkyl alcohols, salts of w-fluoroalkanoic acids, w-fiHOl'O- alkyl nitriles, w-fluoroalkyl esters, w-fluoroalkyl ethers, w-fluoroalkyl acetals, w-fluoroalkanoic acid amides, wfluoroalkyl hydrazides, w-fiuoroalkyl ketones, w-fluoroalkyl aldehydes and w-fiuoroalkyl amines.

2. An anti-fouling paint according to claim 1, the alkyl of the fluoroalkyl containing one to twelve carbon atoms.

3. An anti-fouling paint according to claim 2, the alkyl of the fiuoroalkyl containing six carbon atoms.

4. An antifouling paint according to claim 2, the

alkanoic group of the fluoroalkanoic radical containing six carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS Rudd Nov. 22, 1949 OTHER REFERENCES 

1. AN ANTI-FOULING PAINT CONSISTING OF VARNISH, PIGMENT AND AN W-FLUOROALKYL COMPOUND SELECTED FROM ALKYL ALCOHOLS, SALTS OF W-FLUOROALKANOIC ACIDS, W-FLUORO ALKYL NITRILES, W-FLUOROALKANOIC ESTERS, W-FLUOROALKYL ETHERS, W-FLUOROALKYL ACETALS, W-FLUOROALKANOIC ACID AMIDES, WFLUOROALKYL HYDRAZIDES, W-FLUOROALKYL KETONES, W-FLUOROALKYL ALDEHYDES AND W-FLUOROALKYL AMINES. 